Chiral Side Groups Trigger Second Harmonic Generation Activity in 3D Octupolar Bipyrimidine‐Based Organic Liquid Crystals

The design of efficient noncentrosymmetric materials remains the ultimate goal in the field of organic second‐order nonlinear optics. Unlike inorganic crystals currently used in second‐order nonlinear optical applications, organic materials are an attractive alternative owing to their fast electro‐optical response and processability, but their alignment into noncentrosymmetric film remains challenging. Here, symmetry breaking by judicious functionalization of 3D organic octupoles allows the emergence of multifunctional liquid crystalline chromophores which can easily be processed into large, flexible, thin, and self‐oriented films with second harmonic generation responses competitive to the prototypical inorganic KH₂PO₄ crystals. The liquid‐crystalline nature of these chiral organic films also permits the modulation of the nonlinear optical properties owing to the sensitivity of the supramolecular organization to temperature, leading to the development of tunable macroscopic materials.     

Click chemistry‐based synthesis of azo polymers for second‐order nonlinear optics

Four linear polymers containing pendant azo moiety were synthesized through click chemistry for second‐order nonlinear optical study. The polymers were found soluble in most of the polar organic solvents such as tetrahydrofuran (THF), chloroform, and dimethyl formamide (DMF). The polymers showed thermal stability up to 300 °C and glass transition temperatures (T_g) in the range of 120–140 °C. The molecular weights (M_w) of these polymers (measured by gel permeation chromatography) were in the range 37,900–55,000 g/mol. The polymers were found to form optically transparent films by solution casting from THF solution. Order parameters were calculated from UV–vis absorption spectra. The morphology changes in the films after poling were characterized by atomic force microscopy. The angular dependence, temperature dependence, and time dependence of second harmonic generation (SHG) intensity were obtained by using 1064 nm Nd:YAG laser. The SHG intensity remained unchanged up to 95 °C. At room temperature, it remained stable up to 8 days after initial drop of about 14%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Second harmonic generation and polar order in thin films of polyesters

A series of optically active main chain polyesters were synthesized by high temperature polycondensation from biphenolic azo chromophores with azobenzene-4,4'-dicarbonylchloride and 1,4:3,6-dianhydro-D-sorbitol ([!]_D²⁵=+42.5°). The second harmonic generation of the polyesters is studied in thin films. The polar order in films is determined from the UV-visible absorption spectra. The variation in SHG intensity with chiral monomer concentration is explained as a function of polar order. The polymers with chiral units showed good second harmonic efficiency. The intensity of second harmonic light (532 nm) increased with angle of incidence and indicated the polar order in the plane of the film. The SH signal also showed good temporal stability.     

NH4Be2BO3F2 and γ‐Be2BO3F: Overcoming the Layering Habit in KBe2BO3F2 for the Next‐Generation Deep‐Ultraviolet Nonlinear Optical Materials

KBe₂BO₃F₂ (KBBF) is still the only practically usable crystal that can generate deep‐ultraviolet (DUV) coherent light by direct second harmonic generation (SHG). However, applications are hindered by layering, leading to difficulty in the growth of thick crystals and compromised mechanical integrity. Despite efforts, it is still a great challenge to discover new nonlinear optical (NLO) materials that overcome the layering while keeping the DUV SHG available. Now, two new DUV NLO beryllium borates have been successfully designed and synthesized, NH₄Be₂BO₃F₂ (ABBF) and γ‐Be₂BO₃F (γ‐BBF), which not only overcome the layering but also can be used as next‐generation DUV NLO materials with the shortest type I phase‐matching second‐harmonic wavelength down to 173.9 nm and 146 nm, respectively. Significantly, γ‐BBF is superior to KBBF in all metrics and would be the most outstanding DUV NLO crystal.     

Designing Silicates as Deep‐UV Nonlinear Optical (NLO) Materials using Edge‐Sharing Tetrahedra

Discovering new deep‐ultraviolet (DUV) nonlinear optical (NLO) materials is currently a great challenge. The reported DUV NLO materials are almost exclusively borates or phosphates. Silicates—the largest constituent of the earth's crust—are excluded owing to their weak second harmonic generation (SHG) response. We report a silicate, Li₂BaSiO₄, with edge‐sharing LiO₄–SiO₄ tetrahedra that achieves the balance between a short UV absorption edge, below 190 nm, and a large SHG response, 2.8×KDP. The SHG intensity is the largest for silicates without second‐order Jahn–Teller cations, and exceeds that of non‐isomorphic Li₂SrSiO₄ by more than an order of magnitude. As such Li₂BaSiO₄ may be seen as a promising DUV‐UV NLO material. This research indicates that edge‐sharing tetrahedra is a new design parameter for discovering new DUV NLO materials.     

Magnetic‐Structure‐Stabilized Polarization in an Above‐Room‐Temperature Ferrimagnet

Above‐room‐temperature polar magnets are of interest due to their practical applications in spintronics. Here we present a strategy to design high‐temperature polar magnetic oxides in the corundum‐derived A₂BB′O₆ family, exemplified by the non‐centrosymmetric (R3) Ni₃TeO₆‐type Mn²⁺₂Fe³⁺Mo⁵⁺O₆, which shows strong ferrimagnetic ordering with T_C=337 K and demonstrates structural polarization without any ions with (n?1)d¹⁰ns⁰, d⁰, or stereoactive lone‐pair electrons. Density functional theory calculations confirm the experimental results and suggest that the energy of the magnetically ordered structure, based on the Ni₃TeO₆ prototype, is significantly lower than that of any related structure, and accounts for the spontaneous polarization (68 μC cm^?2) and non‐centrosymmetry confirmed directly by second harmonic generation. These results motivate new directions in the search for practical magnetoelectric/multiferroic materials.     

A Chiral Thermochromic Ferroelastic with Seven Physical Channel Switches

Switchable materials play an invaluable role in signal processing and encryption of smart devices. The development of multifunctional materials that exhibit switching characteristics in multiple physical channels has attracted widespread attention. Now, two chiral thermochromic ferroelastic crystals (S‐CTA)₂CuCl₄ and (R‐CTA)₂CuCl₄ (CTA=3‐chloro‐2‐hydroxypropyltrimethylammonium) have been prepared with switchable properties in dielectricity, conductivity, second harmonic generation (SHG), piezoelectricity, ferroelasticity, chiral, and thermochromic properties. Compared with traditional phase‐transition materials with switching features, thermochromism brings additional spectral encryption possibilities for future information processing. To the best of our knowledge, this is the first chiral thermochromic ferroelastic that exhibits switching properties in seven physical channels. This work is expected to promote further exploration of multifunctional molecular switchable materials.     

Chiral crystal of a C2v‐symmetric 1,3‐diazaaulene derivative showing efficient optical second harmonic generation

Achiral nonlinear optical (NLO) chromophores 1,3‐diazaazulene derivatives, 2‐(4′‐aminophenyl)‐6‐nitro‐1,3‐diazaazulene (APNA) and 2‐(4′‐N,N‐diphenylaminophenyl)‐6‐nitro‐1,3‐diazaazulene (DPAPNA), were synthesized with high yield. Despite the moderate static first hyperpolarizabilities (β₀) for both APNA [(136 ± 5) × 10^?30 esu] and DPAPNA [(263 ± 20) × 10^?30 esu], only APNA crystal shows a powder efficiency of second harmonic generation (SHG) of 23 times that of urea. It is shown that the APNA crystallization driven cooperatively by the strong H‐bonding network and the dipolar electrostatic interactions falls into the noncentrosymmetric P2₁2₁2₁ space group, and that the helical supramolecular assembly is solely responsible for the efficient SHG response. To the contrary, the DPAPNA crystal with centrosymmetric P‐1 space group is packed with antiparalleling dimmers, and is therefore completely SHG‐inactive. 1,3‐Diazaazulene derivatives are suggested to be potent building blocks for SHG‐active chiral crystals, which are advantageous in high thermal stability, excellent near‐infrared transparency and high degree of designing flexibility. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Synthesis,Structure, and Properties of Cadmium(II) Centered Chiral Coordination Polymer based on (R)‐6‐(1‐Carboxyethoxy)‐2‐naphthoic Acid

A cadmium chiral coordination polymer, formulated as [Cd(R‐cna)]_n ( 1 ‐D) was constructed under hydrothermal method. Single‐crystal X‐ray diffraction analysis indicated that 1 ‐D exhibited a 2D layered structure with a point symbol of (4⁷ · 6³). 1 ‐D was further characterized by infrared spectra, powder X‐ray diffraction (PXRD), elemental analysis, thermogravimetric analysis (TGA), and circular dichroism spectra (CD). The second‐harmonic generation (SHG) property was investigated. It was also found that the luminescence of 1 ‐D can be quenched by iron ions and trinitrotoluene, indicating its potential application as luminescence sensing material.     

Synthesis and properties of a second‐order nonlinear optical side‐chain polyimide

A thermal stable aromatic polyimide (PI) with side‐chain second‐order nonlinear optical (NLO) chromophores has been developed. The PI was prepared by the ring‐opening polyaddition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride with a new diamine having two N‐ethyl‐N‐[4‐[(6‐chlorobenzothiazol‐2‐yl)diazenyl]phenyl]‐2‐aminoethanol units as the NLO chromophore, followed by poling during or after the thermal imidization process. The resulting PI had number and weight‐average molecular weights (M_n, M_w) of 25,000 and 80,000, respectively, and a relatively high glass transition temperature of 180°C. The second harmonic coefficient (d₃₃) of PI at the wavelength of 1.064 μm was 138 pm/V (329.6 × 10⁻⁹ esu) and remained unchanged at elevated temperatures. The corona poling process of the NLO‐substituted poly(amic acid) to the PI was also studied in detail by measuring the second harmonic generation (SHG) from the polymer films. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1321–1329, 1999     

Large Second Harmonic Generation (SHG) Effect and High Laser‐Induced Damage Threshold (LIDT) Observed Coexisting in Gallium Selenide

A big challenge for nonlinear optical (NLO) materials is the application in high power lasers, which needs the simultaneous occurrence of large second harmonic generation (SHG) and high laser induced damage threshold (LIDT). Herein we report the preparation of a new Ga₂Se₃ phase, which shows the SHG intensities of around 2.3 times and the LIDT of around 16.7 times those of AgGaS₂ (AGS), respectively. In addition, its IR transparent window ca. 0.59–25 μm is also significantly wider than that of AGS (ca. 0.48–≈11.4 μm). The occurrence of the strong SHG responses and good phase‐matching indicate that the structure of the new Ga₂Se₃ phase can only be non‐centrosymmetric and have a lower symmetry than the cubic γ‐phase. The observed excellent SHG and phase‐matching properties are consistent with our diffraction experiments and can be well explained by using the orthorhombic models obtained through our high throughput simulations.     

Synthesis and properties of novel Y‐type nonlinear optical polyimides with high thermal stability of second harmonic generation

2,4‐Bis‐(3,4‐dicarboxyphenylcarboxyethoxy)‐1‐(2,2‐dicyanovinyl)benzene dianhydride (4) was prepared and reacted with 4,4′‐oxydianiline, 4,4′‐diaminobenzanilide and 4,4′‐(hexafluoroisopropylidene)dianiline to yield novel Y‐type polyimides 5‐7 containing 2,4‐dioxybenzylidenemalononitrile groups as nonlinear optical (NLO) chromophores, which constitute parts of the polymer backbone. The resulting polyimides 5‐7 are soluble in polar solvents such as dimethylsulfoxide and N,N‐dimethylformamide. Polymers 5‐7 showed a thermal stability up to 330 °C in thermogravimetric analysis thermograms with T_g values obtained from differential scanning calorimetry thermograms in the range 179–194 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at the 1064 nm fundamental wavelength were around 5.56 × 10^?9 esu. The dipole alignment exhibited exceptionally high thermal stability even at 20 °C higher than the glass‐transition temperature there was no SHG decay below 215 °C because of the partial main‐chain character of polymer structure, which is acceptable for NLO device applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3078–3087, 2008     

Interfacial polarization phenomena in organic molecular films

Electrostatic phenomena occurring at the interface between metal/organic and organic/organic materials are discussed from the viewpoint of dielectrics physics. Focusing on two important origins of surface polarization phenomena, orientational ordering of polar molecules and displacement of excess charges at the interface, surface polarization phenomena of organic thin films are discussed. To define the orientational order of polar molecules, orientational order parameters are introduced, and surface polarization due to the alignment of dipoles is expressed. The generation of Maxwell displacement current (MDC) and optical second harmonic generation (SHG) that are specific for surface organic monomolecular films are discussed, and some experimental evidence are shown. As an extension of the concept of surface Fermi level introduced to discuss the electrostatic phenomena due to electron transfer at the interface between metal-organic insulators, the surface Fermi level is extended to the discussion on the electrostatic phenomena of organic semiconductor materials on metals. In this paper, some experimental evidence of surface polarization originating from polar molecules and displacement of excess charges are shown. After that, with consideration of these surface phenomena, single electron tunneling of organic films are briefly discussed in association with surface polarization phenomena.     

The Use of Second‐Harmonic Generation to Study Diffusion through Films under a Liquid Phase

Knowledge of the diffusion of chemicals through buried films is important for a wide variety of systems—from sensing to drug delivery. Herein, we show that second‐harmonic generation (SHG) can be used to follow the diffusion through a thin film buried under a liquid in situ. More specifically, the diffusion of 4‐(4‐diethylaminostyryl)‐1‐methylpyridinium iodide through zeolite precursor films of different thickness is followed. The diffusion coefficients are calculated according to Fick’s law.     

Deep‐Ultraviolet Nonlinear Optics in a Borate Framework with 21‐Ring Channels

A new borate LiBa₃(OH)[B₉O₁₆][B(OH)₄], which combines the uniform porosity of open‐frameworks with the extraordinary NLO properties of borates, has been obtained under hydrothermal conditions by using mixed lithium and barium ions as templates. The framework displays an acs‐type net with large 21‐ring channels. The second harmonic generation (SHG) measurement shows that it is a type I phase‐matchable material with a strong SHG signal intensity about 3.1 times that of KDP (KH₂PO₄). UV/Vis–NIR diffuse reflectance analysis indicates that the compound has a wide transparency range with the short‐wavelength absorption edge below 200 nm. These characteristics reveal that the compound is a promising deep‐UV nonlinear optical material.     

Molecular design,synthesis, and nonlinear optical properties of novel T‐type polyimides with exceptionally high thermal stability of the second harmonic generation

2,5‐Bis‐(3,4‐dicarboxyphenylcarboxyethoxy)‐4′‐nitrostilbene dianhydride was prepared and reacted with 1,4‐phenylenediamine, 4,4′‐oxydianiline, 4,4′‐diaminobenzanilide, and 4,4′‐(hexafluoroisopropylidene)dianiline to yield unprecedented novel T‐type polyimides ( 4 – 7 ) containing 2,5‐dioxynitrostilbenyl groups as nonlinear optical chromophores, which constituted parts of the polymer backbones. 4 – 7 were soluble in polar solvents such as acetone and N,N‐dimethylformamide. They showed thermal stability up to 300 °C in thermogravimetric analysis thermograms; the glass‐transition temperatures obtained from differential scanning calorimetry thermograms were around 153 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at the 1064‐cm^?1 fundamental wavelength were around 4.35 × 10^?9 esu. The dipole alignment exhibited exceptionally high thermal stability even at 45 °C higher than the glass‐transition temperature, and there was no SHG decay below 200 °C because of the partial main‐chain character of the polymer structure, which was acceptable for nonlinear optical device applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3189–3199, 2004     

A Displacive‐Type Metal Crown Ether Ferroelectric Compound: Ca(NO3)2(15‐crown‐5)

Following the Curie symmetry principle and Aizu rule, we discovered there is a centrosymmetric‐to‐noncentrosymmetric phase transition in Ca(NO₃)₂(15‐crown‐5) at T_c=205 K. The transition was confirmed by differential scanning calorimetry and second harmonic generation measurements. The transition gives rise to excellent ferroelectricity, such as a giant dielectric anomaly, with faster polarization switching (5×10^?5 s) of up to 10⁷ times without showing fatigue. The ferroelectric mechanism is attributable to the coordination environmental distortion of the central Ca atom. This finding can throw light on the further research in metal–organic ferroelectrics.     

Chiral Thin Films of Metal Oxide

In this paper, we describe for the first time the synthesis of new chiral nanosized metal oxide surfaces based on chiral self‐assembled monolayers (SAMs) coated with metal oxide (TiO₂) nanolayers. In this new type of nanosize chiral surface, the metal oxide nanolayers enable the protection of the chiral self‐assembled monolayers while preserving their enantioselective nature. The chiral nature of the SAM/TiO₂ films was characterized by variety of unique techniques, such as second‐harmonic generation circular dichroism (SHG‐CD), quartz crystal microbalance, and chiral adsorption measurements with circular dichroism spectroscopy. The chiral resolution abilities of the SAMs coated with metal oxide (TiO₂) nanolayers were investigated in the crystallization of a racemic mixture of threonine and glutamic acid. Our proposed methodology for the preparation of nanoscale chiral surfaces described in this article could open up opportunities in other fields of chemistry, such as chiral catalysis.     

Cation‐Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep‐Ultraviolet Nonlinear Optical Materials

The development of new nonlinear optical (NLO) materials for deep‐ultraviolet (DUV) applications is in great demand. However, the synthesis of an ideal DUV NLO crystal is a serious challenge. Herein, three new alkali‐metal fluorooxoborates, AB₄O₆F (A=K, Rb, and Cs, and a mixed cation between two of them), were successfully synthesized by cation regulation. It is found that all reported compounds exhibit short UV absorption edges (<190 nm), and show second harmonic generation (SHG) responses ranging from 0.8 to 1.9 KH₂PO₄ (KDP). Interestingly, by judicious selection of the A‐site alkali‐metal cations, the arrangement of NLO‐active structural units is fine‐tuned to an optimal configuration, which contributes to large SHG responses.     

Pb2BO3Cl: A Tailor‐Made Polar Lead Borate Chloride with Very Strong Second Harmonic Generation

A meticulously designed, polar, non‐centrosymmetric lead borate chloride, Pb₂BO₃Cl, was synthesized using KBe₂BO₃F₂ (KBBF) as a model. Single‐crystal X‐ray diffraction revealed that the structure of Pb₂BO₃Cl consists of cationic [Pb₂(BO₃)]⁺ honeycomb layers and Cl^? anions. Powder second harmonic generation (SHG) measurements on graded polycrystalline Pb₂BO₃Cl indicated that the title compound is phase‐matchable (type I) and exhibits a remarkably strong SHG response, which is approximately nine times stronger than that of potassium dihydrogen phosphate, and the largest efficiency observed in materials with structures similar to KBBF. Further characterization suggested that the compound melts congruently at high temperature and has a wide transparency window from the near‐UV to the mid‐IR region.